JP6888552B2 - Manufacturing method of thermoplastic resin - Google Patents

Description

The present invention relates to a thermoplastic resin having excellent dimensional stability and hue during molding.

In recent years, electronic devices such as digital cameras, smartphones, and tablets have become widespread, and demand for small camera modules is increasing. Plastic lenses are preferably used for these camera modules rather than glass lenses. The reason is that plastic lenses can be used in various shapes such as thin and aspherical surfaces, are inexpensive, and can be easily mass-produced by injection molding.

Resins with various structures that can replace glass have been developed for optical lenses, and various monomers have been studied as raw materials. Optical transparent resins, especially optical lenses made of thermoplastic transparent resins, have the advantage that they can be mass-produced by injection molding and that aspherical lenses can be easily manufactured, and are currently used as camera lenses. ing. As the transparent resin for optics, for example, polycarbonate composed of bisphenol A (BPA) was the mainstream, but a polymer having a fluorene skeleton such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF). (Patent Documents 1 and 2) have been developed. Furthermore, the present inventors have developed a resin using a dihydroxy compound having a binaphthalene skeleton as a raw material monomer as a material having a high refractive index and low birefringence (Patent Document 3).

Resins using these dihydroxy compounds having a binaphthalene skeleton as a raw material monomer are suitable for optical materials, but have a problem that they have a large saturated water absorption rate and dimensional changes during molding are likely to occur. Further, if the saturated water absorption rate is high, a long drying time is required at the time of molding, which causes coloring. Therefore, a resin that is useful as an optical material and has a low saturated water absorption rate is required.

International Publication No. 2007/142149 International Publication No. 2011/010741 International Publication No. 2014/073496

Provided is a method for producing a thermoplastic resin having a low saturated water absorption rate.

As a result of diligent studies on such a problem, the present inventors have solved the above problem by setting the content of a specific dihydroxy compound in the dihydroxy compound having a specific vinaphthalene skeleton within a certain range. And arrived at the present invention. That is, the present invention is, for example, as follows.

（式中、Ｘはそれぞれ独立に、炭素数１〜４のアルキレン基である。）

［２］ 前記ジヒドロキシ化合物は、下記式（２）で表される化合物をさらに含有する、［1］に記載の製造方法。

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数５〜２０のシクロアルキル基、炭素数５〜２０のシクロアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基およびハロゲン原子からなる群から選択され；
Ｘはそれぞれ独立に、炭素数２〜８のアルキレン基であり；
ｎはそれぞれ独立に、１〜５の整数である。）
［３］ 前記熱可塑性樹脂の重量平均分子量が、３５，０００〜７０，０００である、［１］または［２］に記載の製造方法。
［４］ 前記ジヒドロキシ化合物における前記式（Ａ）で表される化合物の重量が、前記式（１）で表されるジヒドロキシ化合物の１００重量部に対して、３００ｐｐｍ以下である、［１］〜［３］のいずれかに記載の製造方法。
［５］ 前記ジヒドロキシ化合物における前記式（Ｂ）で表される化合物の重量が、前記式（１）で表されるジヒドロキシ化合物の１００重量部に対して、１００ｐｐｍ以下である、［１］〜［４］のいずれかに記載の製造方法。
［６］ 前記ジヒドロキシ化合物における前記式（Ｃ）で表される化合物の重量が、前記式（１）で表されるジヒドロキシ化合物の１００重量部に対して、１００ｐｐｍ以下である、［１］〜［５］のいずれかに記載の製造方法。
［７］ 前記式（１）で表されるジヒドロキシ化合物の純度が９９％以上である、［１］〜［６］のいずれかに記載の製造方法。
［８］ 前記熱可塑性樹脂はポリカーボネート樹脂、ポリエステル樹脂、およびポリエステルカーボネート樹脂からなる群から選択される、［１］〜［７］のいずれかに記載の製造方法。
［９］ 前記熱可塑性樹脂はポリカーボネート樹脂である、［８］に記載の製造方法。
［１０］ 前記反応物は炭酸ジエステルをさらに含む、［１］〜［９］のいずれかに記載の製造方法。
［１１］ 前記熱可塑性樹脂の飽和吸水率が、０．３９重量％以下である、［１］〜［１０］のいずれかに記載の製造方法。
［１２］ ［１］〜［１１］のいずれかに記載の製造方法で得られた熱可塑性樹脂を用いることを特徴とする、光学素子の製造方法。
［１３］ ［１］〜［１１］のいずれかに記載の製造方法で得られた熱可塑性樹脂を用いることを特徴とする、光学レンズの製造方法。
［１４］ ［１］〜［１１］のいずれかに記載の製造方法で得られた熱可塑性樹脂を用いることを特徴とする、光学フィルムを製造方法。[1] A method for producing a thermoplastic resin by reacting a reactant containing a dihydroxy compound.
The dihydroxy compound contains a dihydroxy compound represented by the following formula (1).
The total weight of the compound represented by the following formula (A), the compound represented by the following formula (B), and the compound represented by the following formula (C) in the dihydroxy compound is represented by the above formula (1). A production method in which the amount is 1500 ppm or less with respect to 100 parts by weight of the dihydroxy compound.

(In the formula, X is an alkylene group having 1 to 4 carbon atoms independently.)

[2] The production method according to [1], wherein the dihydroxy compound further contains a compound represented by the following formula (2).

(In the formula, R _{1 to} R ₄ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 5 to 20 carbon atoms, and 5 to 20 carbon atoms. Selected from the group consisting of cycloalkoxyl groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms and halogen atoms;
Each of X is an alkylene group having 2 to 8 carbon atoms independently;
n is an integer of 1 to 5 independently of each other. )
[3] The production method according to [1] or [2], wherein the thermoplastic resin has a weight average molecular weight of 35,000 to 70,000.
[4] The weight of the compound represented by the formula (A) in the dihydroxy compound is 300 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1), [1] to [ 3] The manufacturing method according to any one of.
[5] The weight of the compound represented by the formula (B) in the dihydroxy compound is 100 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1), [1] to [1] to [ 4] The manufacturing method according to any one of.
[6] The weight of the compound represented by the formula (C) in the dihydroxy compound is 100 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1), [1] to [ 5] The manufacturing method according to any one of.
[7] The production method according to any one of [1] to [6], wherein the purity of the dihydroxy compound represented by the formula (1) is 99% or more.
[8] The production method according to any one of [1] to [7], wherein the thermoplastic resin is selected from the group consisting of a polycarbonate resin, a polyester resin, and a polyester carbonate resin.
[9] The production method according to [8], wherein the thermoplastic resin is a polycarbonate resin.
[10] The production method according to any one of [1] to [9], wherein the reaction product further contains a carbonic acid diester.
[11] The production method according to any one of [1] to [10], wherein the saturated water absorption rate of the thermoplastic resin is 0.39% by weight or less.
[12] A method for manufacturing an optical element, which comprises using the thermoplastic resin obtained by the manufacturing method according to any one of [1] to [11].
[13] A method for manufacturing an optical lens, which comprises using the thermoplastic resin obtained by the manufacturing method according to any one of [1] to [11].
[14] A method for producing an optical film, which comprises using the thermoplastic resin obtained by the production method according to any one of [1] to [11].

According to the present invention, it is possible to obtain a thermoplastic resin having a low saturated water absorption rate and which is unlikely to undergo dimensional changes during molding.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and is arbitrary as long as it does not deviate from the gist of the present invention. Can be changed to.

One embodiment of the present invention is a method for producing a thermoplastic resin by reacting a reactant containing a dihydroxy compound, wherein the dihydroxy compound contains a dihydroxy compound represented by the following formula (1), and the dihydroxy compound is contained. The total weight of the compound represented by the following formula (A), the compound represented by the following formula (B), and the compound represented by the following formula (C) is the dihydroxy compound represented by the above formula (1). The present invention relates to a production method in which the amount is 1500 ppm or less with respect to 100 parts by weight.

The dihydroxy compound represented by the formula (1) contains a plurality of by-product compounds having a dinaphthol structure as impurities produced as a by-product in the process of synthesis. Among the by-product compounds, the present inventors have found that the presence of a compound represented by the formula (A), a compound represented by the formula (B), and / or a compound represented by the formula (C) is present. It has been found that this is a cause of an increase in the saturated water absorption rate of the thermoplastic resin obtained by polymerizing the dihydroxy compound represented by 1) and a decrease in the rate of the polymerization reaction. Then, they have found that the rate of the polymerization reaction can be improved and the saturated water absorption rate of the thermoplastic resin obtained by the polymerization can be lowered by using the raw material in which these compounds are reduced.

One of the advantages of low saturated water absorption is that the dimensional change of the resin during molding is unlikely to occur. Another advantage of the low saturated water absorption rate is that the drying during molding can be performed in a short time, thereby suppressing the coloring of the resin.

Further, according to the production method of the present invention, the rate of the polymerization reaction can be improved. The advantage of improving the polymerization reaction rate is that a high molecular weight thermoplastic resin can be obtained in a short time. Thermoplastic resins having various molecular weights are required according to the diversifying needs of optical materials. Generally, when polymerization is carried out for a long time in order to obtain a high molecular weight resin, the resin is likely to be colored. It is difficult to obtain a thermoplastic resin with little coloring. The production method of the present invention can increase the molecular weight in a short time, and is advantageous for producing a thermoplastic resin as an optical material.

The production method of the present invention comprises a compound represented by the formula (A), a compound represented by the formula (B), and a compound represented by the formula (C) contained in a dihydroxy compound which is a raw material of a thermoplastic resin. The total weight is 1500 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1). When the total weight is 1500 ppm or less, the effect of lowering the saturated water absorption rate of the thermoplastic resin and / or the polymerization reaction rate can be obtained. The total weight of the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) is preferably 1000 ppm or less, more preferably 500 ppm or less. , More preferably 300 ppm or less. The lower limit of the total weight of the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) is preferably as small as possible, for example, 0 ppm, but 1 ppm. The above is also acceptable. The dihydroxy compound represented by the formula (1) usually contains any of the compounds of the formulas (A), (B), and / or (C) produced as a by-product in the synthetic process thereof, and the total content thereof. To be less than 1 ppm is a heavy load in terms of purification technology. Moreover, even if it is less than 1 ppm, there is no significant difference in physical properties as compared with the case where it is 1 ppm.

In a preferred embodiment, the total weight of the compound represented by the formula (A) and the compound represented by the formula (B) in the dihydroxy compound is 100 parts by weight based on the dihydroxy compound represented by the formula (1). , 1000 ppm or less (more preferably 500 ppm or less, still more preferably 300 ppm or less). Since the compound of the formula (A) and the compound of the formula (B) have an ethylene oxide chain and a phenolic hydroxyl group, they have high polarity and tend to improve hydrophilicity. Therefore, by reducing the contents of the compound of the formula (A) and the compound of the formula (B), the saturated water absorption rate of the obtained thermoplastic resin can be further reduced.

The weight of the compound represented by the formula (A) in the dihydroxy compound is based on 100 parts by weight of the dihydroxy compound represented by the formula (1) from the viewpoint of reducing the saturated water absorption rate of the thermoplastic resin and improving the polymerization rate. It is preferably 300 ppm or less, and more preferably 250 ppm or less. The lower limit is not particularly limited, and is, for example, 0 ppm or 1 ppm or more.

The weight of the compound represented by the formula (B) in the dihydroxy compound is based on 100 parts by weight of the dihydroxy compound represented by the formula (1) from the viewpoint of reducing the saturated water absorption rate of the thermoplastic resin and improving the polymerization rate. It is preferably 500 ppm or less, more preferably 300 ppm or less, further preferably 100 ppm or less, particularly preferably 50 ppm or less, and most preferably 25 ppm or less. The lower limit is not particularly limited, and is, for example, 0 ppm.

The weight of the compound represented by the formula (C) in the dihydroxy compound is based on 100 parts by weight of the dihydroxy compound represented by the formula (1) from the viewpoint of reducing the saturated water absorption rate of the thermoplastic resin and improving the polymerization rate. It is preferably 100 ppm or less, and more preferably 50 ppm or less. The lower limit is not particularly limited, and is, for example, 0 ppm.

The amount of the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) contained in the dihydroxy compound is determined by using high performance liquid chromatography (HPLC). Can be measured. An example of HPLC measurement conditions is as follows.
(HPLC measurement conditions)
-LC measuring device: LC-2010A manufactured by Shimadzu Corporation
-Column: YMC-Pack ODS-AM (4.6 mm diameter x 250 mm, particle size 5 μm)
-Column temperature: 25 ° C
-Mobile phase solvent: pure water / acetonitrile (acetonitrile 20% → 95%)
・ Flow rate: 1.0 mL / min
-Detection method: UV (detection wavelength: 254 nm)
-Sensitivity: 2.5 AU / V (AUXRNG6)
-Sample: 50 mg / 50 mL-acetonitrile

In the embodiment of the present invention, the purity of the dihydroxy compound represented by the formula (1) is 99% or more. In such a case, the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) among the dihydroxy compounds are reduced, and the saturated water absorption rate of the thermoplastic resin is reduced. It is preferable from the viewpoint of reducing the amount of water and improving the polymerization rate.

In the dihydroxy compound, the method for reducing the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) is not particularly limited. For example, a method for purifying the dihydroxy compound represented by the formula (1) after synthesis (for example, washing, filtration, etc.), synthesis conditions for the dihydroxy compound represented by the formula (1) (for example, reaction temperature, reaction time), and the like. The reaction solvent type, the amount of the solvent, and the like can be mentioned.

The method for producing a thermoplastic resin according to an embodiment includes a step of purifying the dihydroxy compound represented by the formula (1). The purification method is not particularly limited, and examples thereof include filtration treatment and / or washing treatment with a washing solvent. The method of the filtration treatment is not particularly limited, but the mesh of the filter is preferably 7 μm or less, more preferably 5 μm or less. The cleaning solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as benzene, ethylbenzene, xylene, and ethyltoluene, aliphatic hydrocarbons such as pentane, hexane, and heptane, and water. Of these, xylene and toluene are preferable. According to such a method, the content of at least one of the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) contained in the dihydroxy compound is significant. Can be reduced to.

The method for producing a thermoplastic resin according to one embodiment is a step of reacting 1,1'-bi-2-naphthol with an alkylene carbonate to obtain a dihydroxy compound of the formula (1). It further comprises a step carried out at a temperature of 110 ° C. or higher (preferably 110 ° C. to 120 ° C., more preferably 110 ° C. to 115 ° C.). According to such a method, the content of at least one of the compound represented by the formula (A), the compound represented by the formula (B), and the compound represented by the formula (C) contained in the dihydroxy compound is significant. Can be reduced to.

The reaction time is preferably 11 hours or less, more preferably 9 to 11 hours, still more preferably 9 to 10 hours. The preferred reaction time can vary depending on the reaction scale. The reaction time refers to the time from when the desired reaction temperature (for example, 110 ° C.) is reached until the alkaline aqueous solution is added.

Hereinafter, the thermoplastic resin obtained by the production method of the present invention will be described.

<Thermoplastic resin>
The thermoplastic resin obtained by the production method of the embodiment of the present invention is produced by reacting a reactant containing the dihydroxy compound represented by the formula (1), and is derived from the dihydroxy compound represented by the formula (1). It includes the structural unit (1)'to be used.

上記式（１）’中、＊は結合部分を示す。

In the above formula (1)', * indicates a joint portion.

A resin made from the compound of the above formula (1) exhibits physical properties such as high refractive index, low Abbe number, high transparency, glass transition temperature suitable for injection molding, and low birefringence, and the resin should be used. As a result, it is possible to obtain an excellent optical component such as an optical lens that has substantially no optical distortion.

As the thermoplastic resin, a polyester resin, a polyester carbonate resin, or a polycarbonate resin is preferable. Above all, it is preferable to contain a polycarbonate resin because it is excellent in heat resistance and hydrolysis resistance. The thermoplastic resin may be contained alone or in combination of two or more.

Optical properties such as the refractive index, Abbe number, and birefringence value are greatly affected by the chemical structure of the constituent units, and the influence of whether the chemical bond between the constituent units is an ester bond or a carbonate bond is relatively small. In addition, the influence of impurities (increase in saturated water absorption rate and decrease in polymerization rate) is also greatly influenced by the chemical structure of the constituent units that make up the resin, and is due to the difference in chemical bonds (ester bond, carbonate bond) between the constituent units. The impact is relatively small.

The thermoplastic resin according to the embodiment of the present invention is produced by reacting a reactant containing a dihydroxy compound. For example, it is produced by polycondensation using a dihydroxy compound containing a dihydroxy compound represented by the formula (1) as a raw material. In the compound represented by the formula (1), the functional group that contributes to polycondensation is an alcoholic hydroxyl group. By polycondensing the compound represented by the formula (1) with a carbonic acid diester and / or a dicarboxylic acid or a derivative thereof, the structural unit derived from the compound represented by the formula (1) is a carbonate bond and / or an ester. It is combined via a bond. By using the dihydroxy compound represented by the formula (1) as a raw material, a thermoplastic resin containing the structural unit (1)'derived from the dihydroxy compound represented by the formula (1) can be obtained.

In the formula (1), X is an alkylene group having 1 to 4 carbon atoms independently. Preferred examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group and a tert-butylene group. Above all, it is preferable that all Xs are ethylene groups because the melt fluidity of the resin at the time of molding is good.

Examples of the dihydroxy compound represented by the formula (1) are 2,2'-bis (1-hydroxymethoxy) -1,1'-binaphthalene and 2,2'-bis (2-hydroxyethoxy) -1,1. Examples thereof include'-binaphthalene, 2,2'-bis (3-hydroxypropyloxy) -1,1'-binaphthalene, 2,2'-bis (4-hydroxybutoxy) -1,1'-binaphthalene and the like. Of these, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene is preferable. These may be used alone or in combination of two or more.

The ratio of the dihydroxy compound of the formula (1) is preferably 1 to 100 mol%, more preferably 30 to 100 mol%, and further, with respect to 100 mol% of the dihydroxy compound used as a raw material of the thermoplastic resin. It is preferably 40 to 100 mol%. The proportion of the dihydroxy compound of the formula (1) is preferably 1 to 100 mol%, more preferably 30 to 100 mol%, based on 100 mol% of all the monomers used as a raw material for the thermoplastic resin. It is more preferably 40 to 100 mol%.

上記式（Ａ）’、（Ｂ）’、または（Ｃ）’中、＊は結合部分を示す。As described above, the dihydroxy compound may include at least one of a compound represented by the formula (A), a compound represented by the formula (B), and a compound represented by the formula (C). When these compounds are contained, they are usually subjected to a polycondensation reaction together with the dihydroxy compound of the formula (1), and the structural unit (A)', which is derived from the compound represented by the formula (A), is contained in the thermoplastic resin. A structural unit (B)'derived from the compound represented by the formula (B) and / or a structural unit (C)' derived from the compound represented by the formula (C) can be incorporated.

In the above formulas (A)', (B)', or (C)', * indicates a connecting portion.

(Other dihydroxy components)
In the present invention, as the dihydroxy component, in addition to the compound represented by the formula (1), other dihydroxy compounds can be used in combination. For example, the dihydroxy compound further contains a dihydroxy compound represented by the formula (2) in addition to the dihydroxy compound represented by the formula (1). By using such a dihydroxy compound as a raw material, the obtained thermoplastic resin is represented by the formula (2) in addition to the structural unit (1)'derived from the dihydroxy compound represented by the formula (1). It further comprises a structural unit (2)'derived from a dihydroxy compound.

上記式（２）’中、＊は結合部分を示す。

In the above formula (2)', * indicates a joint portion.

In the compound represented by the formula (2), the functional group contributing to polycondensation is an alcoholic hydroxyl group or a phenolic hydroxyl group. By using the dihydroxy compound of the formula (2) as a raw material, the obtained thermoplastic resin has a structural unit (2)'derived from the compound represented by the formula (2). The structural unit (2)'derived from the compound represented by the formula (2) contributes to a high refractive index. By including the structural unit (1)'and the structural unit (2)', there is an effect of reducing the birefringence value of the entire resin and reducing the optical distortion of the optical molded product.

In formula (2), R _{1 to} R ₄ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 5 to 20 carbon atoms, and carbon atoms. It represents a cycloalkoxyl group of 5 to 20, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom (F, Cl, Br, I). ^{Among them, compounds in which R 1 to} R ⁴ are hydrogen atoms are preferable because the melt fluidity at the time of molding as an optical lens is good. Further, in order to improve the optical properties of the thermoplastic resin ^{, a compound in which R 1 to} R ² are hydrogen atoms and R ^{3 to} R ⁴ are aryl groups (preferably phenyl groups) having 6 to 20 carbon atoms is also preferable. ..

In the formula (2), each of X independently represents an alkylene group having 2 to 8 carbon atoms. The larger the number of carbon atoms, the lower the melt viscosity of X, and the toughness and moldability are improved. Therefore, a compound having an alkylene group having 2 or more carbon atoms is preferable. On the other hand, as the number of carbon atoms increases, the glass transition temperature decreases. Therefore, from the viewpoint of heat resistance, an alkylene group having 3 or less carbon atoms is preferable. It is more preferable that the number of carbon atoms is 2 to 3 from the viewpoint of achieving both excellent moldability and heat resistance, and in particular, X has 2 carbon atoms in that it is also excellent in terms of refractive index, monomer production and distribution. It is preferably an ethylene group.

In equation (2), n is an integer of 1 to 5 independently. Above all, n is preferably 1 from the viewpoint of excellent thermal stability and availability.

Examples of the compound represented by the formula (2) are 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl). ) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene , 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-Hydroxyethoxy) -3-phenylphenyl) fluorene and the like can be mentioned. Of these, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene and 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene are preferable, and 9,9-bis (4- (2-Hydroxyethoxy) phenyl) fluorene is more preferred. These may be used alone or in combination of two or more.

The total amount of the dihydroxy compound of the formula (1) and the dihydroxy compound of the formula (2) is preferably 50 mol% or more, more preferably 80 mol% or more, based on 100 mol% of the dihydroxy compound used as a raw material of the thermoplastic resin. Is preferable, 90 mol% or more is particularly preferable, and 100 mol% is the most preferable. The molar ratio of the dihydroxy compound of the formula (1) and the dihydroxy compound of the formula (2) (constituent unit (1)'and structural unit (2)') is preferably 20/80 to 80/20, preferably 30/70 to 80. / 20 is more preferable, 30/70 to 50/50 is more preferable, and 40/60 to 50/50 is particularly preferable from the viewpoint of reducing the saturated water absorption rate.

The dihydroxy compound may contain a structural unit derived from a dihydroxy compound other than the compounds of the above formulas (1) and (2). Other dihydroxy compounds include tricyclodecane [5.2.1.0 ^2,6 ] dimethanol, pentacyclopentadecane dimethanol, cyclohexane-1,2-dimethanol, cyclohexane-1,4-dimethanol, cyclohexane. -1,3-dimethanol, decalin-2,6-dimethanol, decalin-2,3-dimethanol, decalin-1,5-dimethanol, 2,3-norbornan dimethanol, 2,5-norbornan dimethanol , 1,3-adamantan dimethanol and other alicyclic dihydroxy compounds; ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-heptandiol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, spiroglycol, etc. Aliphatic dihydroxy compounds; 4,4-bis (4-hydroxyphenyl) propane (ie, bisphenol A), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (ie, bisphenol AP), 2,2 -Bis (4-hydroxyphenyl) hexafluoropropane (ie, bisphenol AF), 2,2-bis (4-hydroxyphenyl) butane (ie, bisphenol B), bis (4-hydroxyphenyl) diphenylmethane (ie, bisphenol BP) ), Bis (4-hydroxy-3-methylphenyl) propane (ie, bisphenol C), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 1 , 1-bis (4-hydroxyphenyl) ethane (ie, bisphenol E), bis (4-hydroxyphenyl) methane (ie, bisphenol F), 2,4'-dihydroxy-diphenylmethane, bis (2-hydroxyphenyl) methane , 2,2-bis (4-hydroxy-3-isopropylphenyl) propane (ie, bisphenol G), 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene (ie, bisphenol) Le M), bis (4-hydroxyphenyl) sulfone (ie, bisphenol S), 2,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 1,4-bis (2- (4-hydroxyphenyl) ) -2-propyl) benzene (ie, bisphenol P), bis (4-hydroxy-3-phenylphenyl] propane (ie, bisphenol PH), 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane (ie, bisphenol TMC), 1,1-bis (4-hydroxyphenyl) cyclohexane (ie, bisphenol Z), 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (ie, bisphenol OCZ) ), 3,3-bis (4-hydroxyphenyl) pentane, 4,4-biphenol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4-hydroxy-2) -Methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4-( 2-Hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) 4-(2-hydroxyethoxy) ) -3-Cyclohexylphenyl) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) pentane, 4,4'-dihydroxy Examples thereof include aromatic dihydroxy compounds such as diphenyl ether and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether.

The other dihydroxy compounds are preferably added in an amount of 20 mol% or less with respect to 100 mol% of the compound of the formula (1), and more preferably 10 mol% or less. Within this range, a high refractive index is maintained.

However, in order to keep the optical strain low, the thermoplastic resin is derived from the resin (first aspect) composed of the structural unit (1)'derived from the dihydroxy compound of the formula (1) or the dihydroxy compound of the formula (1). It is preferable that the resin is composed of the structural unit (1)'and the structural unit (2)' derived from the dihydroxy compound of the formula (2). The thermoplastic resins (polycarbonate resin, polyester resin, polyester carbonate resin) of the first aspect and the second aspect may be mixed and used, or may be mixed and used with other resins. The "resin composed of the constituent unit (1)'and / or the constituent unit (2)'" means that the repeating unit excluding the carbonate-bonded portion and the ester-bonded portion in the resin is the constituent unit (1)'and / or the constituent unit. (2) It means that it consists of'. The polycarbonate bond portion is derived from a carbonate precursor such as phosgene or carbonic acid diester.

The preferred weight average molecular weight of the thermoplastic resin is 10,000 to 100,000. The weight average molecular weight (Mw) of the thermoplastic resin means the polystyrene-equivalent weight average molecular weight, and is measured by the method described in Examples described later. When Mw is 10,000 or more, the brittleness of the molded product is prevented from decreasing. When Mw is 100,000 or less, the melt viscosity does not become too high, the resin can be easily taken out from the mold at the time of molding, the fluidity is good, and the precision of the optical lens or the like in the melted state can be improved. Suitable for required injection molding. More preferably, the weight average molecular weight (Mw) is 35,000 to 70,000, and even more preferably 40,000 to 65,000, from the viewpoint of preventing coloration of the resin and maintaining the strength of the molded product.

When the thermoplastic resin is used for injection molding, the glass transition temperature (Tg) is preferably 95 to 180 ° C, more preferably 110 to 170 ° C, still more preferably 115 to 160 ° C, and particularly preferably 125. ~ 145 ° C. If Tg is lower than 95 ° C., the operating temperature range is narrowed, which is not preferable. On the other hand, if the temperature exceeds 180 ° C., the melting temperature of the resin becomes high, and the resin is likely to be decomposed or colored, which is not preferable. Further, if the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature becomes large in a general-purpose mold temperature controller. Therefore, it is difficult to use a resin having an excessively high glass transition temperature in applications where strict surface accuracy is required for the product, which is not preferable.

The thermoplastic resin preferably has a 5% weight loss temperature (Td) of 350 ° C. or higher as measured at a heating rate of 10 ° C./min as an index of thermal stability to withstand heating during injection molding. If the 5% weight loss temperature is lower than 350 ° C., thermal decomposition during molding is severe and it becomes difficult to obtain a good molded product, which is not preferable.

The thermoplastic resin may have any structure of random, block and alternating copolymer.

Phenol produced during production and carbonic acid diester remaining without reaction are present as impurities in the thermoplastic resin. The phenol content in the thermoplastic resin is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, and is 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. Is particularly preferred. The carbonic acid diester content in the polycarbonate resin or polyester carbonate resin is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. By adjusting the amount of phenol and carbonic acid diester contained in the resin, a resin having physical properties according to the purpose can be obtained. The contents of phenol and carbonic acid diester can be appropriately adjusted by changing the polycondensation conditions and the apparatus. It can also be adjusted by the conditions of the extrusion process after polycondensation.

If the content of phenol or carbonic acid diester exceeds the above range, problems such as a decrease in the strength of the obtained resin molded product and the generation of an odor may occur. On the other hand, if the content of phenol or carbonic acid diester is less than the above range, the plasticity at the time of resin melting may decrease.

The thermoplastic resin according to the embodiment is desired to have as little foreign matter as possible, and it is preferable to perform filtration of the molten raw material, filtration of the catalyst solution, and filtration of the molten oligomer. The mesh of the filter is preferably 7 μm or less, more preferably 5 μm or less. Further, it is also preferable to perform filtration of the produced resin with a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Further, the step of collecting the resin pellets must naturally be in a low dust environment, and is preferably class 6 or less, and more preferably class 5 or less.
Antioxidants, mold release agents, ultraviolet absorbers, fluidity modifiers, crystal nucleating agents, strengthening agents, dyes, antistatic agents, antibacterial agents and the like may be added to the thermoplastic resin of the present invention.

Hereinafter, as an example of the thermoplastic resin, a polycarbonate resin will be described as an example. However, polyester resins and polyester carbonate resins can also be carried out with reference to the description below (polycarbonate resin) and / or using well-known methods.

(Polycarbonate resin)
The polycarbonate resin according to the embodiment is a polycarbonate resin containing a structural unit (1)'derived from the compound represented by the above formula (1) and, if necessary, other structural units described above. The polycarbonate resin is produced by reacting a dihydroxy compound with a carbonic acid precursor such as a carbonic acid diester, and in the polycarbonate resin, each structural unit is bonded via a carbonic acid bond. In one embodiment, the reactants further comprise a carbonate diester in addition to the dihydroxy compound.

Specifically, a dihydroxy compound containing the compound represented by the above formula (1) and a carbonate precursor such as a carbonic acid diester are reacted in the presence of a transesterification catalyst or in the absence of a catalyst by a melt polycondensation method. Can be manufactured.

Examples of the carbonic acid diester include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable. The diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, based on a total of 1 mol of the dihydroxy compound.

An example of the production method is a method in which a dihydroxy compound component is stirred with a carbonic acid diester while being heated and melted in an inert gas atmosphere, and then polymerized while distilling off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. The reaction is depressurized from the beginning to complete the reaction while distilling off the alcohols or phenols produced. Transesterification catalysts can also be used to accelerate the reaction.

In the melt polycondensation in this composition system, a dihydroxy compound containing the compound represented by the formula (1) and a carbonic acid diester are melted in a reaction vessel and then reacted while distilling off a monohydroxy compound produced as a by-product. The reaction time is 200 minutes or more and 500 minutes or less, preferably 250 minutes or more and 450 minutes or less, and particularly preferably 300 minutes or more and 40 minutes or less. The preferred reaction time can vary depending on the reaction scale. The reaction time refers to the time from the time when the raw material is dissolved (that is, the time when stirring becomes possible) to the time when nitrogen is introduced into the reactor after reaching (for example, 180 ° C.).

The reaction may be carried out in a continuous manner or in a batch manner. The reactor used for carrying out the reaction is a vertical type equipped with an anchor type stirring blade, a max blend stirring blade, a helical ribbon type stirring blade, etc., but a horizontal type equipped with a paddle blade, a lattice blade, a glasses blade, etc. It may be an extruder type equipped with a screw. Further, it is preferably carried out to use a reaction device in which these reaction devices are appropriately combined in consideration of the viscosity of the polymer.

As the transesterification catalyst, a basic compound catalyst is used. For example, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds and the like can be mentioned.

Examples of the alkali metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, stearer. Sodium acid, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium phenylated, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, sodium hydrogen phosphate, hydrogen phosphate 2 Potassium, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt or 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt or lithium salt, etc. are used. Be done.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metal compounds. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, acetic acid. Magnesium, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like are used.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxide and salts thereof, amines and the like. Specifically, quaternary ammonium hydroxides having an alkyl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, or an aryl group; Tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; 2-methylimidazole, 2-phenylimidazole, benzoimidazole And other imidazoles; or bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are used.

As other transesterification catalysts, salts of zinc, tin, zirconium, lead and the like may be used, and these may be used alone or in combination. As other ester exchange catalysts, specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, Examples thereof include dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxyde, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II) and lead acetate (IV).

^{These transesterification catalysts are used in a ratio of 1 × 10 -9} to × 10 ^-3 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-4 mol, relative to a total of 1 mol of the dihydroxy compound. Be done.

Two or more types of catalysts may be used in combination. Further, the catalyst itself may be added as it is, or it may be added after being dissolved in a solvent such as water or phenol.

In the melt polycondensation method, melt polycondensation is carried out using the above-mentioned raw materials and catalyst under heating and further under normal pressure or reduced pressure while removing by-products by a transesterification reaction. The catalyst may be present together with the raw materials from the beginning of the reaction, or may be added in the middle of the reaction.

In the method for producing a thermoplastic resin of the present invention, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability after the completion of the polymerization reaction, but it is not always necessary to deactivate the catalyst. When inactivating, a method for inactivating the catalyst by adding a known acidic substance can be preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Kind: Phosphorous acids such as phosphorous acid, phosphoric acid, and phosphonic acid; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-propyl phosphite, di-propyl phosphite Phosphonate esters such as n-butyl, di-hexyl phosphite, dioctyl phosphite, monooctyl phosphate; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorous acid Phosphonates such as dioctyl and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid; phosphonic acid esters such as diethylphenylphosphonate; triphenylphosphine, bis (diphenylphosphino) Phosphines such as ethane; Phosphates such as boric acid and phenylboric acid; Aromatic sulfonates such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid; Organic halides such as chloride, benzoyl chloride and p-toluenesulfonic acid chloride Alkyl sulphate such as dimethyl sulphate; organic halides such as benzyl chloride are preferably used. From the viewpoint of the effect of the deactivator, stability to the resin, and the like, p-toluene or butyl sulfonate is particularly preferable. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol, based on the amount of catalyst. If it is less than 0.01 times the molar amount of the catalyst amount, the deactivating effect becomes insufficient, which is not preferable. On the other hand, if the amount is more than 50 times the molar amount of the catalyst, the heat resistance of the resin is lowered and the molded product is easily colored, which is not preferable.

The kneading of the deactivator may be carried out immediately after the completion of the polymerization reaction, or may be carried out after pelletizing the polymerized resin. In addition to deactivators, other additives (antioxidants, mold release agents, UV absorbers, fluidity modifiers, crystal nucleating agents, strengthening agents, dyes, antistatic agents, antibacterial agents, etc.) Can be added in the same manner.

After catalyst deactivation (after completion of the polymerization reaction when no deactivating agent is added), a step of devolatile removal of the low boiling point compound in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. It may be provided. The temperature at the time of devolatile removal is preferably 230 to 300 ° C, more preferably 250 to 270 ° C. For this step, a horizontal device equipped with a stirring blade having excellent surface renewal ability, such as a paddle blade, a lattice blade, and a glasses blade, or a thin film evaporator is preferably used.

(Other additive ingredients)
Thermoplastic resins include antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, and antibacterial agents, as long as the properties of the present invention are not impaired. , Mold release agents, UV absorbers, plasticizers, compatibilizers and other additives may be added.

Antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,5-di). -Tert-Butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-) tert-Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}- Examples thereof include 2,4,8,10-tetraoxaspiro (5,5) undecane. The content of the antioxidant is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphos Fight, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) ) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite Tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2,4-) Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-) tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) ) -3-Phenyl-Phenylphosphonite and the like. The content of the phosphorus-based processing heat stabilizer is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Sulfur-based processing heat stabilizers include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate). , Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like. The content of the sulfur-based processing heat stabilizer is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

As the release agent, it is preferable that 90% by weight or more thereof is an ester of alcohol and fatty acid. Specific examples of the ester of the alcohol and the fatty acid include an ester of a monohydric alcohol and a fatty acid, a partial ester of a polyhydric alcohol and a fatty acid, or a total ester. As the ester of the monohydric alcohol and the fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Further, as the partial ester or total ester of the polyhydric alcohol and the fatty acid, a partial ester or the total ester of the polyhydric alcohol having 1 to 25 carbon atoms and the saturated fatty acid having 10 to 30 carbon atoms is preferable.

Specifically, examples of the ester of the monohydric alcohol and the saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Partial or total esters of polyhydric alcohol and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, laurate monoglyceride, and pentaerythritol monosteer. Dipentaerythritol such as rate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenylbiphenylate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate. Examples thereof include full ester or partial ester of. Of these, stearic acid monoglyceride and lauric acid monoglyceride are particularly preferable. The content of these release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and 0.02 with respect to 100 parts by weight of the thermoplastic resin. The range of ~ 0.5 parts by weight is more preferable.

The UV absorber is at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. Absorbents are preferred. That is, any of the following ultraviolet absorbers may be used alone, or two or more thereof may be used in combination.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazol, and 2- (2-hydroxy-). 3,5-Dicmylphenyl) Phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1) , 3,3-Tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2-( 2-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazol, 2- (2-hydroxy) -5-tert-octylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazol, 2- (2-hydroxy-4-octoxyphenyl) benzotriazol, 2,2 '-Methylenebis (4-cumyl-6-benzotriazolphenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), 2- [2-hydroxy-3- (3,4) , 5,6-tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazol and the like.

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-hydroxy-4-. Methoxy-5-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone , 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-) Examples thereof include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of triazine-based UV absorbers include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol and 2- (4,6-bis (4,6-bis). 2,4-Dimethylphenyl) -1,3,5-triazine-2-yl) -5-[(octyl) oxy] -phenol and the like can be mentioned.

As the cyclic iminoester-based ultraviolet absorber, 2,2'-bis (3,1-benzoxazine-4-one) and 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) , 2,2'-m-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine-4-one), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene) bis (3,1-benzoxazine-4-one) ), 2,2'-(2-Methyl-p-phenylene) bis (3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1- Benzoxazine-4-one) and 2,2'-(2-chloro-p-phenylene) bis (3,1-benzoxazine-4-one) and the like can be mentioned.

Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl). Examples thereof include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and further preferably 0.02 to 1.0 parts by weight, based on 100 parts by weight of the thermoplastic resin. It is 0.05 to 0.8 parts by weight. Within the range of such a blending amount, it is possible to impart sufficient weather resistance to the thermoplastic resin depending on the application.

In addition to the above-mentioned thermoplastic resin, it may be combined with other resins as long as the characteristics of the present invention are not impaired. That is, the thermoplastic resin of the present invention may be in the form of a resin composition containing a plurality of types of resins. The resin composition contains at least a thermoplastic resin containing 1 to 100% by weight of the repeating unit represented by the formula (1).

Examples of other resins include:
Polyethylene, polypropylene, polyvinyl chloride, polystyrene, (meth) krill resin, ABS resin, polyamide, polyacetal, polycarbonate (but not including structural unit (1)'), polyphenylene ether, polyester (however, structural unit (1)' (Does not contain), polyester carbonate (but does not contain constituent unit (1)'), polyphenylene sulfide, polyimide, polyether sulfone, polyether ether ketone, fluororesin, cycloolefin polymer, ethylene / vinyl acetate co-weight Combined, epoxy resin, silicone resin, phenol resin, unsaturated polyester resin, polyurethane.

The content of the other resin that may be contained is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on the total mass of the thermoplastic resin containing the structural unit derived from the dihydroxy compound of the above formula (1). .. If the content of the other resin is too large, the compatibility may be deteriorated and the transparency of the resin composition may be lowered.

(Physical characteristics of thermoplastic resin)
The thermoplastic resin of the present invention (molded product made from a thermoplastic resin) has a saturated water absorption rate of 0.39% by weight or less, preferably 0.38% by weight or less. The saturated water absorption rate of the resin can be measured by the method described in Examples described later.

The thermoplastic resin of the present invention (molded product made from a thermoplastic resin) has a YI of 19 or less, preferably 18 or less, and more preferably 17 or less. The YI value of the resin can be measured by the method described in Examples described later.

(Molded body)
A molded product (for example, an optical element) can be manufactured using the thermoplastic resin of the present invention. For example, it is molded by an arbitrary method such as an injection molding method, a compression molding method, an extrusion molding method, or a solution casting method. The optical element manufactured by using the thermoplastic resin according to the embodiment is preferably used for a lens, a prism, or the like.

The molded products produced by these methods are used for various glazing applications, automobile lamp lenses, lamp covers, optical lenses, transparencies, name plates, indicator lights and the like. Further, the film produced by such a method is suitably used as a placel substrate or a retardation film for flat panel display substrate applications. The placel substrate is used unstretched, but in order to be used as a retardation film, it is stretch-oriented in at least one axial direction so as to have optimum birefringence characteristics to form a retardation film.

(Optical lens)
An optical lens can be manufactured using the thermoplastic resin of the present invention. Since the optical lens manufactured by using the thermoplastic resin according to the embodiment has a high refractive index and excellent heat resistance, an expensive high refractive index glass lens such as a telescope, binoculars, or a television projector has been conventionally used. It can be used in various fields and is extremely useful. If necessary, it is preferably used in the form of an aspherical lens. Since it is possible to eliminate spherical aberration with a single lens in an aspherical lens, it is not necessary to remove spherical aberration by combining a plurality of spherical lenses, resulting in weight reduction and reduction in production cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

The optical lens is molded by an arbitrary method such as an injection molding method, a compression molding method, or an injection compression molding method. By using the thermoplastic resin according to the embodiment, it is possible to more easily obtain a high-refractive-index, low-birefringence aspherical lens that is technically difficult to process with a glass lens.

When the optical lens of the present invention is manufactured by injection molding, it is preferably molded under the conditions of a cylinder temperature of 230 to 270 ° C. and a mold temperature of 100 to 140 ° C. Due to these molding conditions, it has excellent physical properties as an optical lens and also has a function to cut wavelengths in the ultraviolet region. Therefore, when used as a lens for a digital camera, ultraviolet rays can be transmitted to the image sensor without using an ultraviolet filter. The effect can be prevented. On the contrary, when the resin composition of the present invention is used as an ultraviolet filter, it is possible to take a clear photograph without deteriorating the image quality of the photograph taken because the transparency is very high.

Further, since the resin of the embodiment has high fluidity, it can be an optical lens having a thin wall, a small size, and a complicated shape. As a specific lens size, the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further preferably 0.1 to 2.0 mm. The diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm.

A coat layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens of the present invention, if necessary. The antireflection layer may be a single layer or a multi-layer structure, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride. Further, the optical lens of the present invention may be molded by any method such as mold molding, cutting, polishing, laser machining, electric discharge machining, and edging. Furthermore, mold molding is more preferable.

In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment must naturally be a low dust environment, preferably class 6 or less, and more preferably class 5 or less.

(Optical film)
An optical film can be produced using the thermoplastic resin of the present invention. The optical film produced by using the thermoplastic resin according to the embodiment is excellent in transparency and heat resistance, and is therefore suitably used for a film for a liquid crystal substrate, an optical memory card, and the like.

The "sheet" is generally a thin, flat product whose thickness is small for its length and width, and the "film" is extremely small in thickness and maximum thickness compared to its length and width. A thin, flat product with an arbitrary limitation, usually supplied in the form of a roll. However, in the present specification, "sheet" and "film" are not clearly distinguished, and both are used interchangeably.

The film formed from the thermoplastic resin of the present invention has good heat resistance and hue. For example, the resin composition is dissolved in an organic solvent such as methylene chloride, tetrahydrofuran, or dioxane to form a casting film. A gas barrier film and a solvent-resistant film are attached to both sides of the film, and it is suitably used as a film for a liquid crystal substrate (plastica substrate) or a film for a liquid crystal display such as a retardation film together with a transparent conductive film and a polarizing plate. , Tablets, smartphones, handy terminals, various display elements, etc. can be advantageously used.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Production example of polycarbonate resin Polycarbonate resin was evaluated by the following method.

1) Polystyrene-equivalent weight average molecular weight (Mw):
A calibration curve was prepared using GPC, tetrahydrofuran as a developing solvent, and standard polystyrene having a known molecular weight (molecular weight distribution = 1). It was calculated from the retention time of GPC based on this calibration curve.

2) HPLC measurement conditions BHEBN, compound (A), compound (B), content of compound (C) -LC measuring device: LC-2010A manufactured by Shimadzu Corporation
-Column: YMC-Pack ODS-AM (4.6 mm diameter x 250 mm, particle size 5 μm)
-Column temperature: 25 ° C
-Mobile phase solvent: pure water / acetonitrile (acetonitrile 20% → 95%)
・ Flow rate: 1.0 mL / min
-Detection method: UV (detection wavelength: 254 nm)

Unless otherwise specified, the measurement result is the area percentage value corrected by excluding the solvent in HPLC.

3) Saturated water absorption rate (%): The saturated water absorption rate was measured according to JIS-K-7209 with a disk (diameter 40 mm, thickness 3 mm) obtained by press-molding the obtained polycarbonate resin.
4) YI: Pellets were filled in a quartz glass cell and measured according to JIS K 7373: 2006 by a reflection measurement method using a formula difference meter (SE-2000 manufactured by Nippon Denshoku Co., Ltd.).

<Synthesis example 1>
In a glass reactor equipped with a stirrer, cooler, and thermometer, 1,1'-bi-2-naphthol; 18.082 g (0.063 mol), ethylene carbonate; 12.652 g (0.144 mol). ), Potassium carbonate; 1.5 g and 20 g of toluene were charged, the temperature was raised to 115 ° C. to form a slurry, and then the reaction was carried out at 115 ° C. for 10 hours. After diluting 18 g of toluene with this reaction mixture, the organic solvent phase containing the reaction mixture was washed with 30 g of 10% sodium hydroxide solution, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase was reflux-dehydrated, cooled to room temperature, filtered, and dried to obtain white crystals of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. The HPLC purity was 99.66%, compound (A) was 250 ppm, compound (B) was 30 ppm, and compound (C) was not detected. (BHEBN-1)

<Synthesis example 2>
The reaction was carried out in the same manner as in Synthesis Example 1 except that the reaction was carried out at 110 ° C. for 10 hours to obtain white crystals of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. The HPLC purity was 99.76%, compound (A) was 210 ppm, and compounds (B) and (C) were not detected. (BHEBN-2)

<Synthesis example 3>
The reaction was carried out in the same manner as in Synthesis Example 1 except that the reaction was carried out at 105 ° C. for 12 hours to obtain white crystals of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. The HPLC purity was 98.76%, compound (A) was 480 ppm, compound (B) was 950 ppm, and compound (C) was 200 ppm. (BHEBN-3)

The analysis results of the dihydroxy compounds obtained in Synthesis Examples 1 to 3 are shown in Table 1.

<Example 1>
BHEBN-1 obtained in Synthesis Example 1; 20.360 g (0.054 mol), 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter sometimes abbreviated as "BPEF") 32.954 g (0.075 mol), diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"); 28.521 g (0.133 mol), and sodium hydrogen carbonate as a catalyst; 6 μ mol / mol (carbonate). Sodium hydrogen hydrogen is the number of moles relative to the total of BHEBN-1 and BPEF, and was added in the form of a 0.1 wt% aqueous solution) in a 500 mL glass reaction vessel equipped with a stirrer and a distiller, and a nitrogen atmosphere of 760 Torr. Under, heated to 180 ° C. After 10 minutes from the start of heating, complete dissolution of the raw material was confirmed, and stirring was started. Then, the mixture was stirred for 110 minutes under the same conditions. At this time, it was confirmed that the by-produced phenol was started to be distilled. After that, the degree of decompression was adjusted to 20 Torr, and at the same time, the temperature was raised to 200 ° C. at a rate of 60 ° C./hr. Then, the reaction was carried out by keeping the temperature at that temperature for 20 minutes. Further, the temperature was raised to 230 ° C. at a rate of 75 ° C./hr, and 10 minutes after the completion of the temperature rise, the degree of decompression was reduced to 1 Torr or less over 1 hour while maintaining the temperature. Then, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr, and the reaction was further carried out under stirring for 20 minutes. After completion of the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out. The evaluation of the obtained resin is shown in Table 2.

<Example 2>
BHEBN-1 obtained in Synthesis Example 1; 19.787 g (0.053 mol), 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (hereinafter abbreviated as "BPPEF") 39.756 g (0.067 mol), DPC; 26.078 g (0.122 mol), and sodium hydrogen carbonate as a catalyst; 6 μ mol / mol (sodium hydrogen carbonate is BHEBN-1 and BPPEF). The number of moles relative to the total (added in the state of a 0.1 wt% aqueous solution) was placed in a glass reaction vessel equipped with a stirrer and a distiller, and heated to 180 ° C. under a nitrogen atmosphere of 760 Torr. After 10 minutes from the start of heating, complete dissolution of the raw material was confirmed, and stirring was started. Then, the mixture was stirred for 110 minutes under the same conditions. At this time, it was confirmed that the by-produced phenol was started to be distilled. After that, the degree of decompression was adjusted to 20 Torr, and at the same time, the temperature was raised to 200 ° C. at a rate of 60 ° C./hr. Then, the reaction was carried out by keeping the temperature at that temperature for 20 minutes. Further, the temperature was raised to 230 ° C. at a rate of 75 ° C./hr, and 10 minutes after the completion of the temperature rise, the degree of decompression was reduced to 1 Torr or less over 1 hour while maintaining the temperature. Then, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr, and the reaction was further carried out under stirring for 20 minutes. After completion of the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out. The evaluation of the obtained resin is shown in Table 2.

<Example 3> The reaction was carried out in the same manner as in Example 1 except that BHEBN-2 obtained in Synthesis Example 2 was used. The evaluation of the obtained resin is shown in Table 2.

<Example 4>
The reaction was the same as in Example 2 except that BHEBN-2 obtained in Synthesis Example 2 was used. The evaluation of the obtained resin is shown in Table 2.

<Example 5>
As raw materials, BHEBN-1 obtained in Synthesis Example 1; 14.450 g (0.039 mol), 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF); 40.000 g (0). .091 mol), diphenyl carbonate (DPC); 28.521 g (0.133 mol) and sodium hydrogen carbonate as a catalyst; 6 μ mol / mol (sodium hydrogen carbonate is the number of moles relative to the total of BHEBN-1 and BPEF). Yes, the reaction was carried out in the same manner as in Example 1 except that (added in the state of 0.1 wt% aqueous solution) was used. The evaluation of the obtained resin is shown in Table 2.

<Example 6>
As raw materials, BHEBN-1 obtained in Synthesis Example 1; 23.000 g (0.061 mol), BPEF; 18.000 g (0.041 mol), DPC; 22.500 g (0.105 mol) and as a catalyst. Sodium hydrogen carbonate; 6 μmol / mol (sodium hydrogen carbonate is the number of moles with respect to the total of BHEBN-1 and BPEF and was added in the state of a 0.1 wt% aqueous solution). It reacted in the same way. The evaluation of the obtained resin is shown in Table 2.

<Example 7>
As raw materials, BHEBN-1 obtained in Synthesis Example 1; 12,000 g (0.032 mol), 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (BPPEF); 44 .000 g (0.074 mol), DPC; 23.400 g (0.109 mol) and sodium hydrogen carbonate as catalyst; 6 μ mol / mol (sodium hydrogen carbonate is the number of moles relative to the total of BHEBN-1 and BPPEF. Yes, the reaction was carried out in the same manner as in Example 2 except that (added in the state of 0.1 wt% aqueous solution) was used.

<Example 8>
As raw materials, BHEBN-1 obtained in Synthesis Example 1; 20.000 g (0.053 mol), BPPEF; 21.000 g (0.036 mol), DPC; 19.600 g (0.091 mol) and as a catalyst. Sodium hydrogen carbonate; 6 μmol / mol (sodium hydrogen carbonate is the number of moles with respect to the total of BHEBN-1 and BPPEF and was added in the state of 0.1 wt% aqueous solution), except for Example 2 and It reacted in the same way.

<Comparative example 1>
The reaction was the same as in Example 1 except that BHEBN-3 obtained in Synthesis Example 3 was used. The evaluation of the obtained resin is shown in Table 2.

<Comparative example 2>
The reaction was the same as in Example 2 except that BHEBN-3 obtained in Synthesis Example 3 was used. The evaluation of the obtained resin is shown in Table 2.

<Comparative example 3>
BHEBN-3 obtained in Synthesis Example 3; 18.120 g (0.048 mol), 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF); 29.899 g (0.068 mol). ), Diphenyl carbonate (DPC); 25.600 g (0.120 mol), and sodium hydrogen carbonate as a catalyst; 6 μmol / mol (sodium hydrogen carbonate is the number of moles relative to the sum of BHEBN-1 and BPEF. , 0.1 wt% aqueous solution) was placed in a glass reaction vessel equipped with a stirrer and a distiller, and heated to 180 ° C. under a nitrogen atmosphere of 760 Torr. After 10 minutes from the start of heating, complete dissolution of the raw material was confirmed, and stirring was started. Then, the mixture was stirred for 110 minutes under the same conditions. At this time, it was confirmed that the by-produced phenol was started to be distilled. After that, the degree of decompression was adjusted to 20 Torr, and at the same time, the temperature was raised to 200 ° C. at a rate of 60 ° C./hr. Then, the reaction was carried out by keeping the temperature at that temperature for 20 minutes. Further, the temperature was raised to 230 ° C. at a rate of 75 ° C./hr, and 10 minutes after the completion of the temperature rise, the degree of decompression was reduced to 1 Torr or less over 1 hour while maintaining the temperature. Then, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr, and the reaction was further carried out under stirring for 40 minutes. After completion of the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out. The evaluation of the obtained resin is shown in Table 2.

<Comparative example 4>
BHEBN-1 obtained in Synthesis Example 1; 17.800 g (0.048 mol), 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (hereinafter abbreviated as "BPPEF") 36.420 g (0.062 mol), DPC; 23.646 g (0.110 mol), and sodium hydrogen carbonate as a catalyst; 6 μ mol / mol (sodium hydrogen carbonate is BHEBN-1 and BPPEF). The number of moles relative to the total (added in the state of 0.1 wt% aqueous solution) was placed in a glass reaction vessel equipped with a stirrer and a distiller, and heated at 180 ° C. under a nitrogen atmosphere of 760 Torr. did. After 10 minutes from the start of heating, complete dissolution of the raw material was confirmed, and stirring was started. Then, the mixture was stirred for 110 minutes under the same conditions. At this time, it was confirmed that the by-produced phenol was started to be distilled. After that, the degree of decompression was adjusted to 20 Torr, and at the same time, the temperature was raised to 200 ° C. at a rate of 60 ° C./hr. Then, the reaction was carried out by keeping the temperature at that temperature for 20 minutes. Further, the temperature was raised to 230 ° C. at a rate of 75 ° C./hr, and 10 minutes after the completion of the temperature rise, the degree of decompression was reduced to 1 Torr or less over 1 hour while maintaining the temperature. Then, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr, and the reaction was further carried out under stirring for 40 minutes. After completion of the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out. The evaluation of the obtained resin is shown in Table 2.

ＢＰＥＦ ：９，９‐ビス（４‐（２‐ヒドロキシエトキシ）フェニル）フルオレン
ＢＰＰＥＦ：９、９‐ビス（４‐（２‐ヒドロキシエトキシ）‐３‐フェニルフェニル）フルオレン
ＢＨＥＢＮ：２，２’‐ビス（２‐ヒドロキシエトキシ）‐１，１’‐ビナフタレン
ＢＰＡ：２，２‐ビス（４‐ヒドロキシフェニル）プロパン
ＤＰＣ ：ジフェニルカーボネート
Table 2 shows the composition, Mw (weight average molecular weight), saturated water absorption rate, and YI of the resins obtained in the above Examples and Comparative Examples.

BPEF: 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene BPPEF: 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene BHEBN: 2,2'-bis (2-Hydroxyethoxy) -1,1'-binaphthalene BPA: 2,2-bis (4-hydroxyphenyl) propane DPC: diphenyl carbonate

The saturated water absorption of the polycarbonate resins obtained in Examples 1 to 8 using the raw materials having the reduced content of the compounds of the formulas (A) to (C) is as low as 0.35 to 0.39% by weight. Understand.
In particular, when the raw material (BHEBN-2) in which the content of the compounds of the formulas (A) to (C) is remarkably reduced is used (Examples 3 and 4), the saturated water absorption rate of the resin is remarkably lowered. You can see that.
On the other hand, it can be seen that the saturated water absorption rate of the polycarbonate resins obtained in Comparative Examples 1 to 4 having a large content of the compounds of the formulas (A) to (C) is as high as 0.40% by weight or more.

Further, Examples 1 to 8 using the raw materials having a reduced content of the compounds of the formulas (A) to (C) are obtained polycarbonate as compared with Comparative Examples 1 and 2 using the dihydroxy compounds having the same structure. It was found that an increase in the molecular weight of the resin and an excellent hue (low YI value) were obtained.

Further, Examples 1 to 4 in which the molar ratio of the dihydroxy compound of the formula (1) and the dihydroxy compound of the formula (2) (constituent unit (1)'/ structural unit (2)') is 30/70 to 50/50. , 5 and 7 (particularly Examples 1 to 4 in which the molar ratio is 40/60 to 50/50) have a reduced saturated water absorption rate as compared with Examples 6 and 8 using dihydroxy compounds having the same structure. It is confirmed that it is.

Further, in Comparative Examples 3 and 4, a high molecular weight polycarbonate resin was obtained by lengthening the polymerization reaction time as compared with Comparative Examples 1 and 2, but it was confirmed that the hue was inferior (high YI value). To.

2. Film production example The film was evaluated by the method shown below.

(1) Total light transmittance and haze For the total light transmittance and haze, use a haze meter (“HM-150” manufactured by Murakami Color Technology Research Institute Co., Ltd.), JIS K-7361-1: 1997, JIS. Measured according to K-7136: 2000.

(2) Glass transition temperature Measured by a differential thermal scanning calorimeter (DSC) (Measuring equipment: Hitachi High-Tech Science Co., Ltd. DSC7000X).

(3) Surface shape The surface shape of the light diffusing film was evaluated by the arithmetic mean roughness. The arithmetic mean roughness was calculated as follows by creating a roughness curve using a small surface roughness measuring machine (Mitsutomo Co., Ltd., "Surftest SJ-210"). From the created roughness curve, the range of the reference length (l) (average line direction) is extracted, the X axis is taken in the direction of the average line of the extracted part, and the Y axis is taken in the direction orthogonal to the X axis, and the roughness is taken. When the curve was represented by y = f (x), the value (μm) obtained by the following equation was defined as the arithmetic average roughness (Ra). Here, the "reference length (l) (average line direction)" indicates the reference length of the roughness parameter based on JIS B 0601: 2001 (ISO 4287: 1997).

(5) Refractive index A film having a thickness of 0.1 mm was measured by the method of JIS-K-7142 using an Abbe refractometer (23 ° C., wavelength 589 nm).

(6) Abbe number (ν)
For a film having a thickness of 0.1 mm, the refractive index at wavelengths of 486 nm, 589 nm and 656 nm was measured at 23 ° C. using an Abbe refractometer, and the Abbe number was calculated using the following formula.
ν = (nD-1) / (nF-nC)
nD: Refractive index at a wavelength of 589 nm
nC: Refractive index at wavelength 656 nm
nF: Refractive index at a wavelength of 486 nm

(7) Melt volume rate (MVR)
The obtained resin was vacuum-dried at 120 ° C. for 4 hours, and measured using a melt indexer T-111 manufactured by Toyo Seiki Seisakusho Co., Ltd. under the conditions of a temperature of 260 ° C. and a weight of 2160 g.

<Example 9>
6.20 kg (16.56 mol) of BHEBN, 10.00 kg (22.80 mol) of BPEF, 8.67 kg (40.46 mol) of diphenyl carbonate (DPC), 1.98 × 10-sodium hydrogen carbonate. The reaction was carried out in the same manner as in Example 1 except that 2 g (2.36 × 10-4 mol) and the reactor were changed to 50 L. After completion of the reaction, nitrogen was introduced into the reactor, and the produced polycarbonate resin was extracted while pelletizing.

The obtained pellets were melt-extruded at 280 ° C. using a 26 mm twin-screw extruder and a T-die. The extruded molten film was nipped with a first cooling roll made of silicon rubber having a diameter of 200 mm and a second cooling roll made of metal having a diameter of 200 mm which had been matted (arithmetic mean roughness of the surface: 3.2 μm). After shaping the mat pattern on the surface of the film, the film was cooled, and the film was passed through a third cooling roll made of metal having a mirror surface structure, and the single-sided mat film was formed while being picked up by the take-up roll. At this time, the temperature of the first cooling roll is set to 40 ° C., the temperature of the second cooling roll is set to 130 ° C., the temperature of the third cooling roll is set to 130 ° C., and the speed of the cooling roll is adjusted to perform arithmetic on the film surface. The average roughness was set to 3.0 μm.

The evaluation results of the film obtained in Example 9 are shown in Table 3.

From Table 3 above, it is confirmed that the film produced using the polycarbonate resin of the present invention has a high haze, is excellent in transparency, and exhibits a low Abbe number and a high refractive index.

3. 3. Example of manufacturing an optical lens In a thin-walled molded product, the radius of curvature of the convex surface is 5.73 mm, the radius of curvature of the concave surface is 3.01 mm, the size is 4.5 mm in diameter, the diameter of the lens portion is 3 mm, and the center thickness of the lens is 0. Using a mold for forming a 20 mm lens, 10 molded products with a resin temperature of 260 ° C, a mold temperature of Tg-5 ° C, and a holding pressure of 600 kgf / cm ^{2 using a ROBOSHOT S-2000i30A injection molding machine manufactured by Fanac Co., Ltd.} Created.

The obtained optical lens was evaluated by the following method.

[Birefringence evaluation]
The obtained molded product was measured with a birefringence meter (manufactured by Oji Measuring Instruments Co., Ltd .; KOBRA (registered trademark) -CCD / X), and compared by the value of retardation at the measurement wavelength of 650 nm at the center of the lens. The smaller the retardation value, the better the low birefringence, and 20 or more was defined as A, 20 or more and less than 40 was designated as B, 40 or more and less than 60 was designated as C, and 60 or more was designated as D.

[Weld line evaluation]
The obtained molded product was observed with a microscope, and the weld line length generated in the anti-gate direction was measured. If the length of the weld line is less than 0.1 mm, it is A, if it is 0.1 mm or more and less than 0.3 mm, it is B, if it is 0.3 mm or more and less than 0.5 mm, it is C, and if it is 0.5 mm or more, it is D.

<Example 10>
The polycarbonate resin obtained in Example 1 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Example 11>
The polycarbonate resin obtained in Example 2 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Example 12>
The polycarbonate resin obtained in Example 3 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Example 13>
The polycarbonate resin obtained in Example 4 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Comparative example 5>
The polycarbonate resin obtained in Comparative Example 1 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Comparative Example 6>
The polycarbonate resin obtained in Comparative Example 2 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Comparative Example 7>
The polycarbonate resin obtained in Comparative Example 3 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Comparative Example 8>
The polycarbonate resin obtained in Comparative Example 4 was vacuum dried at 120 ° C. for 1 hour to prepare an injection molded product. Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

<Comparative Example 9>
An injection molded product was prepared using pellets of a polycarbonate resin (Iupilon H-4000 manufactured by Mitsubishi Engineering Plastics Co., Ltd .; a polycarbonate resin made of bisphenol A (BPA-HOMO-PC)). Table 4 shows the results of birefringence evaluation and weld line evaluation of the obtained molded product.

From Table 4 above, the optical lens manufactured by using the polycarbonate resin of the present invention had low birefringence (evaluation of B).

Furthermore, the optical lens of the present invention also had a short weld line length (evaluation of A or B). It is presumed that this is due to the good saturated water absorption of the polycarbonate resin of the present invention and the suppression of the generation of decomposition gas when the polycarbonate resin of the present invention is used. Generally, the weld line is affected by factors such as gas accumulation in the mold, molding conditions (molding temperature, mold temperature, pressure, etc.), and generation of decomposition gas. The polycarbonate resin of the present invention can reduce the abundance of OH (water, aromatic OH, etc.) in the system by using a raw material in which the content of the compounds of the formulas (A) to (C) is reduced, and this is an ester. It is presumed that this led to the suppression of replacement and the generation of decomposed gas could be suppressed.
Therefore, by using the polycarbonate resin of the present invention, conventional measures for reducing the weld line length (for example, countermeasures with a mold (installation of a vent, adjustment of the wall thickness of the mold, adjustment of the gate, etc.)). ) Can be reduced, which is advantageous in terms of manufacturing cost and ease of manufacturing.

Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

Claims (12)

A method for producing a polycarbonate resin by reacting a reactant containing a dihydroxy compound.
The dihydroxy compound contains a dihydroxy compound represented by the following formula (1) and 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene.
The total weight of the compound represented by the following formula (A), the compound represented by the following formula (B), and the compound represented by the following formula (C) in the dihydroxy compound is represented by the above formula (1). It is 1500 ppm or less with respect to 100 parts by weight of the dihydroxy compound.
Molar ratio of the formula (1) represented by dihydroxy compound and 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, Ri 40 / 60-50 / 50 der,
The amount of the dihydroxy compound other than the dihydroxy compound represented by the formula (1) and 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene contained in the dihydroxy compound is the above. Ru amount der of 10 mol% or less relative to the dihydroxy compound 100 mol% of the formula (1), the production method.

(In the formula, X is an ethylene group.)

The production method according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 35,000 to 70,000. The invention according to claim 1 or 2, wherein the weight of the compound represented by the formula (A) in the dihydroxy compound is 300 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1). Production method. Any of claims 1 to 3, wherein the weight of the compound represented by the formula (B) in the dihydroxy compound is 100 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1). The manufacturing method according to one item. Any of claims 1 to 4, wherein the weight of the compound represented by the formula (C) in the dihydroxy compound is 100 ppm or less with respect to 100 parts by weight of the dihydroxy compound represented by the formula (1). The manufacturing method according to one item. The production method according to any one of claims 1 to 5, wherein the purity of the dihydroxy compound represented by the formula (1) is 99% or more. The dihydroxy compound represented by the formula (1) is 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene.
The polycarbonate resin contains a structural unit derived from the 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl). The production method according to any one of claims 1 to 6, which comprises a constituent unit derived from fluorene. The production method according to any one of claims 1 to 7 , wherein the reaction product further contains a carbonic acid diester. The production method according to any one of claims 1 to 8 , wherein the saturated water absorption rate of the polycarbonate resin is 0.39% by weight or less. A method for manufacturing an optical element, which comprises using the polycarbonate resin obtained by the manufacturing method according to any one of claims 1 to 9. A method for manufacturing an optical lens, which comprises using the polycarbonate resin obtained by the manufacturing method according to any one of claims 1 to 9. A method for producing an optical film, which comprises using the polycarbonate resin obtained by the production method according to any one of claims 1 to 9.